Ferrocene-Functionalized Cu(I)/Ag(I) Dithiocarbamate Clusters

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• 作者：Pilli V. V. N. Kishore ; Jian-Hong Liao ; Hsing-Nan Hou ; Yan-Ru Lin ; C. W. Liu
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：April 4, 2016
• 年：2016
• 卷：55
• 期：7
• 页码：3663-3673
• 全文大小：544K
• ISSN：1520-510X

文摘

A series of compounds, namely, [Cu₈(μ₄-H){S₂CNMeCH₂Fc}₆](PF₆) (1), [Cu₇(μ₄-H) {S₂CNⁱPrCH₂Fc}₆] (2), [Cu₃{S₂CN(Bz) (CH₂Fc)}₂(dppf)₂](PF₆) (3), and [Ag₂{S₂CNMe(CH₂Fc)}₂(PPh₃)₂] (4) (dppf = 1,1′-bis(diphenylphosphino)ferrocene), supported by multiferrocene assemblies, were synthesized. All the compounds were characterized by ¹H NMR, Fourier transform infrared, elemental analysis, and electrospray ionization mass spectrometry techniques. Single-crystal X-ray structural analysis revealed that 1 is a monocationic octanuclear Cu^I cluster and that 2 is a neutral heptanuclear Cu^I cluster with tetracapped tetrahedral (1) and tricapped tetrahedral (2) geometries entrapped with an interstitial hydride, anchored by six ferrocene units at the periphery of the core. Compounds 3 and 4 comprise trimetallic Cu^I and dimetallic Ag^I cores enfolded by four and two ferrocene moieties. Interestingly both chelating and bridging modes of binding are observed for dppf ligand in 3. Further the formation and isolation of polyhydrido copper clusters [Cu₂₈H₁₅{S₂CNⁱPrCH₂Fc}₁₂](PF₆) (5) and [Cu₂₈H₁₅{S₂CNⁿBu₂}₁₂](PF₆) (7), stabilized by bulky ferrocenyl and n-butyl dithiocarbamate ligands, was demonstrated. They are readily identified by ²H NMR studies on their deuterium analogues, [Cu₂₈D₁₅{S₂CNⁱPrCH₂Fc}₁₂](PF₆) (6) and [Cu₂₈D₁₅{S₂CNⁿBu₂}₁₂](PF₆) (8). Though the structure details as well as spectroscopic characterizations of 5 are yet to be investigated, the compound 7 is fully characterized by variety of spectroscopy including single-crystal X-ray diffraction. The cyclic voltammetry studies for compounds 1, 2, and 4 display irreversible redox peaks for Fe²⁺/Fe³⁺ couple wherein the reduction peaks are not well-resolved due to some adsorption of the complex onto the electrode surface.